Biopolymeric water treatment

ABSTRACT

A method of water treatment includes providing water that includes at least one contaminant. An effective amount of at least one filter media is added to the to the water that includes at least one contaminant. The water and the at least one filter media are agitated to form a homogeneous mixture. A cationic biopolymer is added to the homogeneous mixture of water and the at least one filter media. The water is separated from the at least one contaminant and the at least one filter media.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication No. 62/532,727, filed Jul. 14, 2017, which is incorporatedherein by reference in its entirety.

BACKGROUND

The present disclosure is related to the field of water processing andpurification. More specifically, the present disclosure is related tothe purification of water using polymer additives.

Water may be contaminated with numerous substances considered harmful tohuman or other life. Microorganisms for example from wastewater, canspread disease among humans. While often a secondary effect of nitrateand/or phosphate contamination algae and other aquatic plants can beanother source of contamination. Algae can produce toxins which leachinto the water. Furthermore, dead algae and aquatic plans provide aready food source to other microorganisms and bacteria which are harmfulto humans. Pharmaceuticals or hormones can harm biological processes.Minerals and chemicals with harmful cumulative effects can naturallyoccur or may be present in water distribution systems.

Many industrial or resource extraction operations produce contaminatedwater. These operations may contaminate water with heavy metals,volatile organic compounds (VOCS), polychlorinated biphenyls (BCB_(s)),pharmaceuticals, pesticides, radionuclides, and harmful microorganisms.These and other contaminants must be removed before the water isdischarged or it risks contaminating the environment or freshwaterresources.

Being a well known source of harmful microorganisms, water is oftentreated prior to human consumption. Often drinking water is treated withharsh chemicals in order to eliminate harmful microorganisms that cancause health problems in humans and/or pets. There is growing publicconcern and caution regarding impact on human health from ingesting thechemicals used to treat water. There are similar concerns regarding theimpact of the use of these chemicals on the quality of our naturalenvironment.

BRIEF DISCLOSURE

An exemplary embodiment of a method of water treatment includesproviding water that includes at least one contaminant. An effectiveamount of at least one filter media is added to the to the water thatincludes at least one contaminant. The water and the at least one filtermedia are agitated to form a homogeneous mixture. A cationic biopolymeris added to the homogeneous mixture of water and the at least one filtermedia. The water is separated from the at least one contaminant and theat least one filter media.

In further exemplary embodiments of the method, at least one contaminantis adsorbed from the water that includes at least one contaminant ontothe filter media. The at least one filter media and the at least onecontaminant are coagulated with the cationic biopolymer. The water isseparated from the at least one contaminant and the at least one filtermedia by mechanical separation. The water is separated from the cationicbiopolymer at the same time that the water i s separated from the atleast one contaminant and the at least one filter media.

In exemplary embodiments of the method, the filter media includes atleast two of: carbon, aragonite, bentonite, zeolite and diatomite. Themethod may include determining a chemical content of the at least onecontaminant in the water. The method may further include selecting theat least one filter media based upon the determined chemical content. Inembodiments, a turbidity of the water may be measured. The effectiveamount of the at least one filter media may be determined from themeasured turbidity of the water. The effective amount of the cationicbiopolymer may be determined from a measured turbidity of the waterafter the addition of the at least one filter media.

In additional exemplary embodiments, the cationic biopolymer is added tothe water as a cationic biopolymer solution. The cationic biopolymer mayinclude chitosan or a chitosan derivative. The chitosan derivative maybe selected from chitosan citrate, chitosan oligosaccharide, chitosanacetate, chitosan malate, and chitosan formate.

In further exemplary embodiments of the method, the water separated fromthe at least one contaminant and the at least one filter media isfiltered after separation. The water separated from the at least onecontaminant and the at least one filter media may be treated with UVlight after separation. The removed at least one contaminant and the atleast one filter media may be collected for use as a fertilizer.

In exemplary embodiments, the at least one contaminant is a firstcontaminant and the at least one filter media is a first filter media.An effective amount of a second filter media is added to the waterseparated from the first contaminant and the first filter media. Thewater and the second filter media are agitated to form a homogeneousmixture. Chitosan or a chitosan derivative is added to the homogeneousmixture of water and the at second filter media. The water is separatedfrom a second contaminant and the second filter media. The secondcontaminant may be adsorbed from the water onto the second filter media.The second filter media and the second contaminant may be coagulatedwith the chitosan or the chitosan derivative.

In still further exemplary embodiments of the method, filter media hasan average particle size less than one millimeter. The filter media mayhave an average particle size less than 100 micrometers. The filtermedia may include a geopolymer.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a flow chart that depicts an exemplary embodiment of a methodof water treatment using biopolymers.

FIG. 2 is a system diagram of an exemplary embodiment of a watertreatment system.

DETAILED DISCLOSURE

The present disclosure relates to the treatment of water usingbiopolymer additives to purify the water from plant, bacteria, viruses,and other microorganism contaminants. The present disclosure alsorelates to systems and processes of water treatment for not only plant,bacteria, and other microorganism contaminants, but to remove othercontaminants including, but not limited to: dissolved solids, suspendedsolids, heavy metals, volatile organic compounds (VOC's), radionuclides,pesticides, and pharmaceuticals.

Embodiments as disclosed herein incorporate the addition of abiopolymer, or a biopolymeric mixture in the water treatment process.The biopolymer of chitosan will be used herein in its exemplarycapacity, although it will be recognized that other biopolymers havingsimilar properties may be suitable for use in other embodiments.

Chitosan is an abundant biopolymer consisting of randomly distributedbeta (1->4)-linked D-Glucosamine (deacetylated unit) andN-acetyl-D-Glucosamine (acetylated unit) obtained by the partialdeacetylation of chitin. Chitin is found mainly in the exoskeletons ofcrustaceans and insects, as well as in fungi (e.g. mushrooms andyeasts). At the present time, chitin obtained from shellfish shellsstands as the most sustainable and abundant source of chitin in theworld, therefore the most abundant and sustainable source of chitosan inthe world. Chitin is the second most abundant biopolymer in the world.While chitin is abundant, much of it is discarded as waste from theharvesting or removal of shellfish for industrial, commercial, orconsumption purposes.

In embodiments, chitosan and/or chitosan derivatives with or withoutfurther materials may be added into a water treatment process as anatural herbicide and pesticide, and to promote efficiency in the watertreatment process. Chitosan and chitosan oligosaccharide derivatives cankill harmful bacteria, fungus, fungus gnats, botrytis, thrips, syllids,white flies, citrus greening disease, aphids, nematodes, etc. Whileexhibiting these anti-microbial properties, chitosan and chitosanoligosaccharide are biocompatabile, biodegradable, and hypo allergenic.See Further Katiyar, Deepmala, et al. “A Future Perspective in CropProtection: Chitosan and its Oligosaccharides,” Adv Plants Agric Res2014, 1(1):00006; Doares, Steven H., et al. “Oligogalacturonides andchitosan activate plant defensive genes through the octadecanoidpathway,” Proc. Natl. Acad. Sci. USA Vol. 92, pp. 4095-4098, May 1995Colloquium Paper; and Malerba, Massimo, et al. “Chitosan Effects onPlant Systems,” Int. J. Mol. Sci. 2016, 17, 996, all of which are herebyincorporated by reference herein in their entireties.

While the exemplary embodiment of chitosan is used herein, it will berecognized that other biopolymers may also be used in furtherembodiments within the present disclosure. Chitosan has a property ofbeing a coagulant for suspended particles in water. This effect can befurther leveraged in a water treatment process to improve water clarityand removal of accumulated contaminants.

Embodiments of the invention as described herein include a variety ofprocesses by which a biopolymer, and exemplarily a cationic biopolymer(e.g. chitosan or chitosan derivative) is used to treat water to improvethe water quality and elevate the available uses for that water. Otherembodiments as described herein provide processes by which usefulbyproducts of such water treatment are isolated for reuse.

In exemplary embodiments, a cationic biopolymer alone or in combinationwith one or more derivatives of that biopolymer (e.g. chitosanoligosaccharide) is mixed into water for treatment. The combination ofchitosan and chitosan oligosaccharide provides a fuller spectrum ofantimicrobial effect. Chitosan and chitosan oligosaccharide havedifferent but partially overlapping anti-microbial effects, thereforecombination of these two substances provides a complementary effect.

In embodiments, the cationic biopolymer, and any derivatives thereof,are used in a process of water treatment in combination with anotherfilter media. In a first exemplary embodiment, liquid chitosan is usedin combination with at least one additional water filter media to treatwater. In such an embodiment, the combination of biopolymer, biopolymerderivative, and filter media is used in a moving bed bio reactor watertreatment system. In-situ or batch/retort treatment systems may alsoimplement the processes described herein. The filter media used mayinclude but is not limited to: calcium, bentonite, perlite, activatedalumina, redox alloys, activated carbon, diatomite, aragonite, zeolite,attapulgite and ion exchange resins. In exemplary embodiments, thefilter media is a geopolymer. A combination of one or more of the abovefilter media may be selected based upon the known contaminants in thewater to be treated. Exemplary embodiments, include but are not limitedto: carbon for VOC's or Pharmaceuticals; zeolite for Phosphates,Nitrates, VOC's, heavy metals, or oils; activated alumina/redox to raisedissolved oxygen levels and remove metals and VOC's; aragonite toselective phosphate removal or antimicrobial purposes; calcium ormagnesium to additionally increase pH; diatomite (diatomaceous earth)for clarification or antimicrobial properties; bentonite or clay forsolids, heavy metals or oils.

While the disclosure provided herein is not so limited, exemplaryembodiments are provided that use a combination of a biopolymer and ageopolymer media. In more specific embodiments, the biopolymer ischitosan. Geopolymers are inorganic materials that form covalentlybonded amorphous structures. Geopolymers include, but are not limited tosilicate, aluminosilicate, phosphosilicate, ferrosilicate materials.Geopolymers can occur naturally or can be manufactured, manufacturedgeopolymers can also include calcium, fly ash, or organic mineral basedgeopolymers and others. The addition of chitosan to these geopolymermedia produce further a coagulation and flocculation effect when used ina moving bed water treatment system. The concentrations, amounts, andspecific variety of biopolymers (e.g. chitosan/chitosanoligosaccharide/chitosan citrate) may be varied based upon thegeopolymer media used and the specific contaminants targeted during theprocess.

In use, the combined filter media and biopolymer treatment substance ismixed into the untreated water stored exemplarily in a water treatmentreservoir, bioreactor, retort or similar. During the mixing process, themicronized filter media acts as molecular sieves and, in embodiments,ion exchange particles form chemical and mechanical bonds with aspectrum of contaminants while the chitosan promotes the flocculation,coagulation, and separation of the contaminants from the water. Ratherthan using pressure like reverse osmosis, which can require significantenergy expenditure, this process may instead use the repeated localizedexpansion and contraction pressures of mixing/stirring/mechanicalagitation to ensure maximum exposure/absorption/adsorption/ion exchangeto/with the pores/receptor sites of the filter media, which contains thechitosan.

In another exemplary embodiment, multiple stages of water treatment areprovided with filter media and biopolymer combinations. In a multi stageprocess, solids/turbidity can be removed selectively, heavymetals/dissolved metals, VOC's, Pharmaceuticals, microorganisms,nutrients, etc. by a predetermined order of filter media treatments infunnel like manner in order to achieve specific or broad spectrumreduction of contaminants. In an exemplary embodiment of the selectivemulti stage process each stage uses a different biopolymer media (e.g.clay, silicate, etc.) and chitosan polymer combination to remove thecontaminants and flocculate by the media and further coagulate thecontaminants for sequestration and removal. This multi-stage process maybe implemented as a batch process or as an inline process.

As described herein, further examples of water treatment processessequentially treat the water with filter media and then add thebiopolymer to further treat the water, but to also coagulate andfacilitate removal of the filter media entrained in the water to form apotentially usable by-product as described in further detail herein, andto clear the filter media from one stage from the water before theaddition of a subsequent filter media or other water treatmentprocesses.

FIG. 1 is a flow chart that depicts an exemplary embodiment of a method100 of water treatment using biopolymers. FIG. 2 is a system diagram ofan exemplary embodiment of a water treatment system 10. An embodiment ofthe water treatment system 10 may operate to carry out an embodiment ofthe method 100. The water treatment system 10 is exemplarily depicted ina generalized form whereby water may be treated in an inline or in abatch processing manner, for example by changing the dimensions of thecomponents and by operation of valves 12 between the stages. While notdepicted in still further embodiments, gravity feed or pumps between thestages may be used to move the water between stages in a batch treatmentprocess.

At 102, the influent water quality is tested. In an exemplary embodimentthis is performed using a turbidity sensor 14. Exemplarily a turbiditysensor may include a light source and a measurement of the scatteredand/or received light at a light sensor. This information is provided toa controller 16. Turbidity is caused by particles suspended or dissolvedin water that scatter light making the water appear cloudy or murky.Sediment, organic and inorganic matter, organic compounds, algae, andmicroscopic organisms are all causes of turbidity. It will be recognizedthat in other embodiments other or additional water quality measurementsmay be taken and used by the controller 16 as described herein. Theturbidity may exemplarily be measured in the Nephlelometric TurbidityUnit (NTU).

The controller 16 is exemplarily a microcontroller and/or a processorthat is communicatively connected and/or integrated to a computerreadable medium upon which computer readable code in the form ofsoftware or firmware is stored. The microcontroller/processor executesthe computer readable code and operates to carry out the processing andcontrol functions as described in further detail herein. In a batchprocessing system or method, the controller 16 may provide controlsignals to one or more valves 12 to maintain the selective flow of waterthrough the processing stages of the system 10. In embodiments, thecontroller may have predetermined durations of time between operationsof valves 12 in the system 10, or the open and/or closed durations maybe dependent upon the operation of other components of the system 10 asthe system 10 operates to process water as disclosed herein.

The controller 16 operates to determine at 104 at least one filter mediaand/or an amount of filter media to be added to the influent water. Thefilter media and/or filter media amount is determined based upon thewater turbidity and/or other measurement of water quality. It will berecognized that additional water quality or chemical contentmeasurements (and the associated sensors) may be incorporated into theinitial water quality testing and the results provided to the controller16. Such measurements may identify particular chemicals for removal, forexample, phosphorous or nitrogen; other measurements may identify aclass of compound for removal, for example VOC's or hydrocarbons; whilestill other measurements may identify biological, for example algae orbacterial loads for removal. The information from these sensors to thecontroller 16, can enable the controller to determine the types and/oramount of filter media to use to treat the water in this stage of theprocess. The filter media and/or filter media amount may be furtherdetermined based upon a desired quality of the output effluent. In anexemplary embodiment, this occurs in a first stage which may be embodiedin a first mixing chamber 18. The first mixing chamber 18 may be open ateither end in an inline treatment system or may be selectively filled,closed, and drained by operation of associated valves 12.

Depending on the influent water quality, a specific blend of naturalmedia (made to address/reduce specific contaminants and levels) isintroduced/injected into the influent line or vessel in whichcontaminated water is passing or filling. The filter media may bemicronized or otherwise in the form of a fine powder. In an exemplaryembodiment, the filter media average particle size is less than 1 mm,while in other embodiments the filter media average particle size isless than 100 μm, and in still further embodiments the filter mediaaverage particle size is less than 1 μm. In embodiments, the filtermedia is a geopolymer. In exemplary embodiments, particular filter mediamay be preferentially suited for removal of some contaminants ratherthan others. In one embodiment, carbon powder, activated alumina, redoxalloys may be used to remove VOC's, pharmaceuticals, pesticides, heavymetals, etc. In another exemplary embodiment aragonite, pyrrhotite,and/or zeolite may be used to remove phosphates and nitrates.

The filter media may be premixed (if a blend of media) and provided in asupply hopper 20. While not depicted, multiple supply hoppers may beprovided with various filter media and the controller 16 determines anamount and a type from the available filter media types to add to theinfluent water. In an exemplary embodiment, the amount of the filtermedia is determined from the turbidity of the water and/or from anothermeasurement from the testing of the water. The amount and type of mediaused in this stage is exemplarily dependent upon the level and type ofcontaminants present. The filter media is added at 106, exemplarily byoperation of a mechanical feeder 22. The mechanical feeder may include,but is not limited to a pump, a conveyor, a measured dosing apparatus,or a partition for gravity feed thereof In another embodiment, thefilter media is entrained in water and injected by pumping through apipe or hose. The filter media is thereby introduced into influent waterin the first mixing chamber 18.

In an inline system, the flow of the influent water in combination withobstructions and/or baffles to promote circulation may be sufficient tomix the filter media and influent water. In a batch system (or an inlinesystem) further mechanical mixing or agitation is needed to mix thefilter media and influent water at 108. A mixer 24 is provided in thefirst chamber 18 to mix the filter media and the influent water.Mechanical mixing or agitation may be performed using paddles, pumps,impellors, stirrers, or the like. Mixing may additionally be performedin other manners, including vibratory or ultrasonically. Whileembodiments may achieve mixing in a variety of ways, in one preferredembodiment, the media is mixed with the water inside the vessel/chamberin a counterclockwise rotation that initiates cavitation and implosioncreated by paddles/pumps/impellors, etc. This rapid mixing (preferablycounterclockwise) allows the media to be evenly dispersed within thevolume of water to be treated. The hydrological mechanics of cavitationand implosion/repeated expansion and contraction allows for maximumcontact and pressure of the media to the water molecules. This maximizesthe absorption, adsorption, and ion exchange capacity of the mediawithin the water being treated. The process as provided herein thereforeuses filter media that moves and is circulated freely through the waterrather than using a membrane or stationary bed of granular or ionexchange resin through which the water is moved.

Once the water and filter media is mixed to a homogenous mixture ofsuspended solids comprised of contaminants, contaminant laden media, andwater within the chamber 18. In an embodiment, the homogeneous mixtureis provided from a first processing stage to a second processing stage,exemplarily by operation of a valve 12 to provide the homogeneousmixture to a second chamber 26. However, it will be recognized thatother embodiments may be implemented with only one chamber, to which thecationic biopolymer is added. At this time, the biopolymer, which may bechitosan or a chitosan derivative (e.g. chitosan oligosaccharide) isadded at 110 from a reservoir 28 to the homogeneous mixture in thesecond chamber 26, for example by operation of a feeder 30, which may bea pump or other mechanical feeder. While in some embodiments, thechitosan or chitosan derivative may be added as a dry volume, in otherembodiments, the chitosan or chitosan derivative is added as a chitosansolution. In embodiments, this has been found to promote faster mixingand coagulative effect.

As noted above, an amount of the chitosan or chitosan derivative neededfor the treatment process may be determined by the controller. Examplesof cationic biopolymers that may be used in embodiments include, but arenot limited to chitosan acetate, chitosan malate, chitosan citrate,chitosan formate, and others as may be recognized by a person ofordinary skill in the art in view of this disclosure. The cationicbiopolymer may be provided in a concentration of 1-3% solutions ofchitosan/chitosan derivative. The amount of the chitosan or chitosanderivative may exemplarily be based upon the turbidity measurement. Inan exemplary embodiment, the dosage of chitosan when paired with naturalmedia for selective or broad spectrum contaminant removal is directlyproportionate to the turbidity (NTU) created by the addition of thenatural media with the water. Heavier solids will require a higherconcentration of the chitosan or chitosan derivative to coagulate andform flocs. It will be recognized that in embodiments, the antimicrobialproperties of chitosan derivatives may be enhanced or mitigated orotherwise selected for or against depending upon a desired microbialload of the outgoing water from the treatment. In an exemplaryembodiment, a stronger antimicrobial compound, for example chitosanacetate, may be used when microbial removal is desired. In otherembodiments, a compound with a weaker antimicrobial effect, for example,chitosan malate, may be used if a higher output microbial count isdesired, for example for a later aerobic or anaerobic digestion or yeastformation use.

It will be recognized that the chitosan/modified chitosan may furtherinclude one or more additives to modify or enhance the properties of thechitosan, including, but not limited to bentonite. The chitosan/modifiedchitosan coagulates the suspended solids/media at 112 to effectivelyseparate the contaminants and contaminant laden media from the cleanwater. These coagulated flocs naturally sink to the bottom and the cleanwater stays on the upper layer of separation within the chamber 26. Theclean water on the top layer can then be separated from the coagulate at112 by draining the water from the top of the vessel or pumping thewater from the top of the vessel to remove the water from the secondchamber 26.

The coagulate may be removed from the bottom of the second chamber 26for example by an auger 32 that operates to direct the coagulate into acollection receptacle 34 for gathering for disposal or reuse. Otherforms of pumps, piping, scraping, screening, or paddles may be used toremove the coagulate. The separated water is filtered at 116 as a finalprocess to remove any further contaminants or coagulate thatinadvertently was pulled from the second chamber 26. The water mayexemplarily be filtered using a the same filter media and biopolymercombination as used in the process above, screening, other mechanicalfiltration using ceramic or microfiber filters, carbon/activated carbonfiltration, gravel, or sand. For example in the case of the treatedwater to be used for drinking/human consumption, then the furtherfiltering may be used. In an exemplary embodiment, filter media ofactivated carbon powder, sand, and diatomaceous earth is added, mixed,coagulated and flocced with the chitosan or chitosan derivative in afinal removal of harmful substances. The water may further be treatedwith UV light 38, for example UV light in the C wavelength band. Thisprocess results in purified treated water effluent 40.

EXAMPLES

In one scenario, water contaminated with phosphate mining tailings istreated. These mining tailings and/or other similar waste stream withhigh total suspended solids (TSS) can be initially treated with thechitosan or chitosan derivative. The suspended solids (colloids) arenegatively charged which prevents the formation of larger masses(flocs), and prevents settling. Introduction of the chitosan or chitosanderivative, which exhibits a positive ionic charge, promotes a processof coagulation, flocculation, and settling. Gypsum and clay particlescan be removed via flocculation/coagulation in this first stage. Thewater enters a second stage/tank that is configured to remove totaldissolved solids (TDS) from the water. Depending upon the elements inthe dissolved solids, a specific media type can be added and mixed intothe water in order to retrieve the specific dissolved solidsconstituents. In this example, a phosphate and/or nitrate specificflocculant/coagulant combo media is introduced and mixed. Exemplarilythe filter media is at least one of aragonite, pyrrhotite, and zeolite(or modified/impregnated zeolite). This filter media is specific tophosphate and attaches to dissolved phosphate in the water andcoagulates, flocculates, separates, and can be removed by gravityseparation, aeration/flotation, skimming/screening, lamella flow, etc.In a further embodiment, the chitosan or chitosan derivative may beadded to the water at this stage as well to facilitate coagulation andremoval of the media laden with trapped particles, including phosphate.As an added benefit, the coagulate results in media loaded withphosphate that, when paired, with aragonite makes a soil stabilizinggrowth boosting plant fuel.

In another scenario, eutrophic water supplies are loaded with nutrientssuch as phosphates and nitrates along with micro algae feeding off ofthe nutrients. Nutrient and algae laden water pose an environmental andpersonal health risk. Algae blooms are also a prime area for bacteriagrowth and disease carrying mosquitoes to reproduce. In an embodiment oftreating this water, the water enters a tank/vessel where media specificto phosphates and nitrates is mixed into the nutrient and algae ladenwater. As noted above, such media may include, but are not limited toaragonite, pyrrhotite, and zeolite. After sufficient mixing, chitosanand/or chitosan derivatives are added into the contaminated water andmixed rapidly. The media (aragonite, diatomite, zeolite, etc.) attachesto the algae and microalgae, as well as the nitrates and phosphates inthe water, then the chitosan solution coagulates the media and nutrientstogether. Here again, the media that is specific to phosphate/nitrateattaches to dissolved phosphate/nitrate in the water and coagulates,flocculates, separates, and can be removed by gravity separation,aeration/flotation, skimming/screening, lamella flow, etc.

In an embodiment, a filter media that includes one part aragonite, twoparts bentonite, and one part zeolite may be used in the treatment ofalgae laden water. In such an embodiment, aragonite helps to bind tonitrate, phosphate, and algal biomass. The bentonite helps with settlingand removal of biomass. The zeolite helps to remove phosphates,nitrates, and algal biomass.

In a further example of treatment of algae laden water, the high-algaewater is pumped into a chamber/vessel where it is mixed with a blend ofnatural media to reduce suspended solids as well as media to selectivelyremove nitrates and phosphates. After the rapid mixing, chitosan and/ormodified chitosan is added via a laminar flow pump, peristaltic pump,dosing meter, etc. to deliver the exact measured dose required tocoagulate and separate the algae, phosphate, nitrates, and media fromthe water. As noted above, the doses of the chitosan or chitosanderivative or of any of the filter media may exemplarily be based uponthe measured turbidity of the water. In a separate additionalchamber/vessel the solids are removed and processed to in order toseparate oil from the algae to be used as biofuel. Harmful cyanotoxinsare removed during this stage using carbon, zeolite, calcium carbonate,etc. The remaining solids are comprised of algae biomass as well asnitrate and phosphate laden natural media. The media used in this stageof the process (example carbon-biochar, aragonite, zeolite, bentonite,etc.) are essential soil building supplements that (among many otherbenefits) prevent nutrient run off/algae blooms.

This exemplary process has the further benefit of sequestering algae,nitrates, and phosphates onto the selected filter media. Thiscombination of the filter media, chitosan, and the removed substancescan be utilized as fertilizer and soil enhancer. This may be applied tothe soil, or as a coating directly onto seeds. When performed locally,this can reduces nutrient overload while improving the soilquality(which can decreases water requirements), and reduces nutrientrun off which reduces harmful algae blooms.

In an exemplary embodiment as discussed above, wherein the sequesteredalgae, nirates, phosphates, and natural filter media are to be collectedand used, then a further processing step or steps may be added. While anembodiment as described above may successfully remove VOC's, pesticides,pharmaceuticals, heavy metals, and/or radionuclides from the influentwater, such contaminants would collect and concentrate in thesequestered algae, nitrates, phosphates, and natural filter media. Ifthat collected substance is to be reused as a fertilizer or soilsupplement, it is desirable to not have the VOC's, pesticides,pharmaceuticals, heavy metals, and/or radionuclides. Therefore, aninitial process stage in which carbon powder, activated alumina, redoxalloys, etc. can be added to the influent water. Those filter media maybe removed by coagulation and separation, for example with the additionof the chitosan or chitosan derivatives. This removed these harmfulcontaminants prior to collection of contaminants with otherwise greaterreuse opportunities/potential/value. This technique may be expandedbeyond two stages as described above to include a “funnel” of stages toremove contaminants in an order of least valuable to most valuable. Thisresults in the most valuable collected contaminants also being the mostpure and free from other less valuable and/or more hazardouscontaminants.

In embodiments, processes as described herein may be used indesalination of water and/or the treatment of brackish salinated water.Zeolite may be used in the geopolymer media in a fluid bed bioreactortreatment system. Chitosan biopolymer used in the biopolymer/geopolymercombination as described above, is also cationic which aids in theadsorption/Ion exchange and absorption of salts and minerals onto thegeopolymer powder (for example bentonite, zeolite, aragonite,attapulgite, calcium, carbonate, etc.) In still further embodiments,bentonite or attapulgite clay or zeolite can be used to remove lithiumsalts from the treated water, while bentonite exemplarily is effectivein phosphate adsorption.

In another embodiment, a unique natural pesticide can be provided usingthe concepts discussed above. In an embodiment, this natural pesticideincludes chitosan, chitosan oligosaccharide, hydrogen peroxide,diatomite, hemp seed oil, bentonite, zeolite, and kelp/kelp extract. Inone embodiment, it has been found that this pesticide mixture isparticularly effective against citrus greening disease which is causedby a bacteria (Candidatus Liberibacter asiaticus) spread by insects,typically the Asian citrus psyllid, outbreaks of which have recentlythreatened citrus crops in Southeastern United States and elsewhere. Itwill be recognized that in other embodiments, more than or fewer thanthe constituent components listed above may be used, while remainingwithin the scope of the present disclosure.

Chitosan is non-water soluble, whereas chitosan oligosaccharide is watersoluble. By combining the two substances, the plants can more readilyabsorb the chitosan and chitosan oligosaccharide while being protectedby the non-water soluble form. This decreases the need for the planttissue to produce chitosanase enzyme in order to break down the chitosanto be absorbed. The chitosan is a polymer (slightly viscous) that cancoat the plant and not be washed away easily by rain, whereas thechitosan oligosaccharide can more easily be absorbed by the plant tissueand roots, therefore boosting immunity extra cellularly andintracellularly as well as exhibiting antimicrobial effects throughoutthe plant.

However, it has been found that chitosan acetate, formed bydeacetylating chitin using acetic acid provides still further advantagesover the use of chitosan alone. The chitosan acetate provides theanti-microbial effect of chitosan noted above, while providing theadditional antimicrobial effects of acetic acid.

Other components of the pesticide mixture noted above further providecomplementary advantages to the chitosan citrate and chitosanoligosaccharide noted above. Hydrogen Peroxide treats root rot, preventsroot infections, and promotes root growth and disease resistance. Thehydrogen peroxide further kills mold and mildew while aerating soil, allof which further enhance plant root health. Diatomite (diatomaceousearth) is a known effective insecticide effective against aphids,thrips, gnats, ants, mites, earwigs, adult flea beetles, cockroaches,snails, and slugs. The microscopic sharp edges of the diatomite damagescell lipid layers causing cells to dry out. Hemp seed oil exhibitsfurther antimicrobial properties, killing bacteria, viruses, fungus,nematodes, mold, and mildew. Bentonite is a complementary additive tochitosan, the combination of which is known to kill gram positive andgram negative bacteria. Bentonite also helps plants to remain hydrated.Zeolites have high absorption capacities and high ion exchangecapacities which make them effective carriers of fungicides andpesticides. Zeolites further provide soil amendment effects, helpingsoil to retain water, which improves nutrient retention in the soil byslowing the release of large cations such as ammonium and potassiumuptake into plants. Kelp extract and/or seaweed extract further providesa source of minerals, vitamins and enzymes that are natural growthstimulants to plants which fuel plant cells to grow, producing stronger,healthier, and disease resistant plants. This also makes the plants moreresistant to stress conditions such as drought or frost, increasedresistance to pests, and increased yields. Kelp/seaweed extracts furthercontain alginates that are sponge like starches which hold waterdroplets near plants roots.

Citations to a number of references are made herein. The citedreferences are incorporated by reference herein in their entireties. Inthe event that there is an inconsistency between a definition of a termin the specification as compared to a definition of the term in a citedreference, the term should be interpreted based on the definition in thespecification.

In the above description, certain terms have been used for brevity,clarity, and understanding. No unnecessary limitations are to beinferred therefrom beyond the requirement of the prior art because suchterms are used for descriptive purposes and are intended to be broadlyconstrued. The different systems and method steps described herein maybe used alone or in combination with other systems and methods. It is tobe expected that various equivalents, alternatives and modifications arepossible within the scope of the appended claims.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to make and use the invention. The patentable scope of the inventionis defined by the claims, and may include other examples that occur tothose skilled in the art. Such other examples are intended to be withinthe scope of the claims if they have structural elements that do notdiffer from the literal language of the claims, or if they includeequivalent structural elements with insubstantial differences from theliteral languages of the claims.

1. A method of water treatment comprising: providing water comprising atleast one contaminant; adding a geopolymer filter media to the water;agitating the water comprising at least one contaminant and thegeopolymer filter media to form a homogeneous mixture; adsorbing the atleast one contaminant from the water onto the geopolymer filter media;adding a cationic biopolymer to the homogeneous mixture of water and thefilter media; coagulating the geopolymer filter media and the at leastone contaminant with the cationic biopolymer to form coagulated flocs;separating the water from the at least one contaminant and thegeopolymer filter media by settling of the coagulated flocs; andremoving the water from the coagulated flocs.
 2. The method of claim 1,wherein the geopolymer filter media comprises a combination of at leastaragonite, bentonite, and zeolite.
 3. The method of claim 1, wherein thecationic biopolymer comprises chitosan or a chitosan derivative.
 4. Themethod of claim 3, wherein the chitosan derivative is selected fromchitosan citrate, chitosan oligosaccharide, chitosan acetate, chitosanmalate, and chitosan formate.
 5. The method of claim 3, wherein thecationic biopolymer comprises chitosan and at least one of: chitosanoligosaccharide, chitosan acetate, and chitosan citrate.
 6. The methodof claim 3, wherein the cationic biopolymer further comprises bentonite.7. The method of claim 3, wherein the cationic biopolymer comprisingchitosan or a chitosan derivative is added as a solution having aconcentration between 1-3% (m/v).
 8. The method of claim 3, furthercomprising: measuring a turbidity of the homogeneous mixture; andselecting a concentration of the cationic biopolymer comprising chitosanor a chitosan derivative based upon the measured turbidity wherein theconcentration increases with increases in the turbidity.
 9. The methodof claim 1, wherein the water is removed from the coagulated flocsduring settling of the coagulated flocs.
 10. The method of claim 1,further comprising: filtering the water removed from the coagulatedflocs; and mechanically collecting the coagulated flocs.
 11. The methodof claim 1, wherein the geopolymer filter media further comprises atleast one additive from: carbon, calcium, perlite, activated alumina,redox alloys, attapulgite, ion exchange resins, diatomite, andpyrrhotite.
 12. The method of claim 1, wherein the at least onecontaminant comprises algae and the geopolymer filter media comprises atleast one of aragonite, pyrrhotite, diatomite, bentonite, and zeolite.13. The method of claim 1, wherein the cationic biopolymer comprises acombination of chitosan oligosaccharide with chitosan or chitosanacetate.
 14. The method of claim 1, wherein the geopolymer filter mediacomprises a geopolymer having an affinity for one or both of phosphateand nitrate.
 15. The method of claim 14, wherein the geopolymer filtermedia comprises at least aragonite and zeolite.
 16. The method of claim15, wherein the geopolymer filter media further comprises at least oneof bentonite and pyrrhotite.
 17. The method of claim 1, furthercomprising initially treating the water comprising at least onecontaminant with chitosan or a chitosan derivative before adding thegeopolymer filter media to the water.
 18. The method of claim 1, whereinthe geopolymer filter media has an average particle size less than onemillimeter.
 19. The method of claim 18, wherein the geopolymer filtermedia has an average particle size less than 100 micrometers.
 20. Themethod of claim 1, wherein the geopolymer filter media comprisesaragonite, bentonite, and zeolite in a ratio of one part aragonite, twoparts bentonite, and one part zeolite.